Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes

Chiral complexes formed by privileged phosphoramidites derived from chiral binol and optically pure Davies’ amines, and copper(II) triflate, silver(I) triflate or silver(I) benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between nitroalkenes and azomethine ylides generated from α-amino acid derived imino esters. These three methods can be conducted at room temperature to afford the exo-cycloadducts (4,5-trans-2,5-cis-4-nitroprolinates) with high diastereoselectivity and high enantioselectivity. In general, the three procedures are complementary but silver catalysts are more versatile and less sensitive to sterically congested starting materials.

Pyrimidine-Derived Prolinamides as Recoverable Bifunctional Organocatalysts for Enantioselective Inter- and Intramolecular Aldol Reactions under Solvent-Free Conditions

Chiral L-prolinamides 2 containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-pyrimidinyl unit are synthesized and used as general organocatalysts for intermolecular and intramolecular aldol reactions with 1,6-hexanedioic acid as a co-catalyst under solvent-free conditions. The intermolecular reaction between ketone–aldehyde and aldehyde–aldehyde must be performed under wet conditions with catalyst (S,S)-2b at 10 °C, which affords anti-aldols with high regio-, diastereo-, and enantioselectivities. For the Hajos–Parrish–Eder–Sauer–Wiechert reaction, both diastereomers of catalyst 2 give similar results at room temperature in the absence of water to give the corresponding Wieland–Miescher ketone and derivatives. Both types of reactions were scaled up to 1 g, and the organocatalysts were recovered by extractive workup and reused without any appreciable loss in activity. DFT calculations support the stereochemical results of the intermolecular process and the bifunctional role played by the organocatalyst by providing a computational comparison of the H-bonding networks occurring with catalysts 2a and 2b.

The International Competitiveness of the Biscayan Iron and Steel Industry (1880-1913)

This study has a double objective: to provide foreign colleagues with an insight into the controversy surrounding the international competitiveness of pig iron produced in Bilbao and also to present previously unpublished documentation regarding the European iron industry, which I have retrieved from the historical archive of Credit Lyonnais of Paris. This information includes the costs of Biscayan, French, British, German and Belgium pig iron broken down into five components (iron ore, coke, flux, labour and other costs), which is useful in determining the reasons why the pig iron from Bilbao became less competitive. The article is made up of three parts. Firstly, I will synthesise the controversy surrounding the competitiveness of the Basque iron and steel industry. Then I will present the itemised costs which provide information to illustrate how Biscayan pig iron was not competitive because it was produced with English coal which was more expensive than that consumed by the European factories located "on top of" or near coal seams. The article will finish with a section that, by way of conclusion, explains the comparative advantage and disadvantage of Bilbao, applying the first model of Alfred Weber's Theory of Industrial Location to three technological advances, occurring between the 1860s and 1913 (malleable iron, Bessemer steel and Thomas steel).

Synthesis of Chromen[4,3-b]pyrrolidines by Intramolecular 1,3-Dipolar Cycloadditions of Azomethine Ylides: An Experimental and Computational Assessment of the Origin of Stereocontrol

Azomethine ylides, generated from imine-derived O-cinnamyl or O-crotonyl salicylaldeyde and α-amino acids, undergo intramolecular 1,3-dipolar cycloaddition, leading to chromene[4,3-b]pyrrolidines. Two reaction conditions are used: (a) microwave-assisted heating (200 W, 185 °C) of a neat mixture of reagents, and (b) conventional heating (170 °C) in PEG-400 as solvent. In both cases, a mixture of two epimers at the α-position of the nitrogen atom in the pyrrolidine nucleus was formed through the less energetic endo-approach (B/C ring fusion). In many cases, the formation of the stereoisomer bearing a trans-arrangement into the B/C ring fusion was observed in high proportions. Comprehensive computational and kinetic simulation studies are detailed. An analysis of the stability of transient 1,3-dipoles, followed by an assessment of the intramolecular pathways and kinetics are also reported.

Primary Amine–2-Aminopyrimidine Chiral Organocatalysts for the Enantioselective Conjugate Addition of Branched Aldehydes to Maleimides

Chiral primary amines containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a pyrimidin-2-yl unit are synthesized and used as general organocatalysts for the Michael reaction of α-branched aldehydes to maleimides. The reaction takes place with 10 mol% organocatalyst loading and hexanedioic acid as cocatalyst in aqueous N,N-dimethylformamide at 10 °C affording the corresponding succinimides in good yields and enantioselectivities. DFT calculations support the stereochemical results and the role played by the solvents.

Enantioselective addition of aryl ketones and acetone to nitroalkenes organocatalyzed by carbamate-monoprotected cyclohexa-1,2-diamines

Enantiomerically pure carbamate-monoprotected trans-cyclohexane-1,2-diamines are used as chiral organocatalysts for the addition of aryl ketones and acetone to nitroalkenes to give enantioenriched β-substituted γ-nitroketones. The reaction was performed in the presence of 3,4-dimethoxybenzoic acid as an additive, in chloroform as the solvent at room temperature, achieving enantioselectivities up to 96%. Theoretical calculations are used to justify the observed sense of the stereoinduction.

Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α-disubstituted, to maleimides catalysed by chiral carbamate-monoprotected trans-cyclohexane-1,2-diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.

El lenguaje gráfico de Eduardo Chillida como aportación conceptual para la identidad tipográfica de la Universidad del País Vasco —UPV/EHU—

Este proyecto de investigación financiado por la Universidad del País Vasco/Euskal Herriko Unibertsitatea —UPV/EHU-PES 11/31—, a través de su programa de investigación estratégica, tiene como objetivo la creación de la tipografía de identidad visual corporativa de la Universidad del País Vasco —UPV/EHU—, cuyo inicio conceptual para dotar de unas características de identidad visual corporativa a la UPV/EHU, ha sido planteado desde las especulaciones estéticas sobre la forma, materializadas por Eduardo Chillida. En la producción gráfica de este artista encontramos una sutil coincidencia con principios vitales para la creación tipográfica, en cuanto al planteamiento de formas dinámicas y constructivas, en las que el rigor geométrico es vencido por una suerte de organicidad que parte del núcleo mismo de la estructura —«cursus»—, por: la fuerza vital que imprime la acción modulada del gesto —«ductus»—; por la dialéctica entre lo lleno y lo vacío —forma/contraforma—, por el impulso y la espontaneidad — carácter—, o por la afirmación de un lenguaje plástico en la cultura diferenciada del medio en el que se vive —identidad—.

Bifunctional primary amine 2-aminobenzimidazole organocatalyst anchored to trans-cyclohexane-1,2-diamine in enantioselective conjugate additions of aldehydes

Bifunctional chiral primary amine 8 containing an (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-benzimidazole unit is used as a general organocatalyst for the Michael addition of α,α-branched aldehydes to nitroalkenes and maleimides. The reactions take place, with 20 mol % of catalyst in dichloromethane at rt for nitroalkenes and with 15 mol % catalyst loading in toluene at 10 °C for maleimides, in good yields and enantioselectivities. DFT calculations demonstrate the bifunctional character of this organocatalyst activating the aldehyde by enamine formation and the Michael acceptor by double hydrogen bonding.

La sostenibilidad en la planificación territorial de escala regional en España: estudio de casos

En las dos últimas décadas, la expresión «desarrollo territorial sostenible» se ha incorporado con éxito en los documentos de ordenación del territorio, hasta convertirse en un principio rector principal. El objetivo de este artículo es analizar la incorporación de los principios de sostenibilidad en la planificación territorial española, valorando los resultados prácticos que ello ha significado. Se ha realizado un análisis de las leyes y planes de ordenación del territorio de escala regional, destacando en cuatro casos de estudio (País Vasco, Navarra, Andalucía y Comunidad Valenciana) por la relevancia que este principio rector ha cobrado en sus procesos de planificación territorial. Se ha completado la información con la realización de entrevistas a actores clave de la ordenación del territorio en esos espacios regionales. Los resultados muestran que, a pesar de las buenas intenciones que incluyen los textos de leyes y planes, por lo común, el proceso de integración de la sostenibilidad a la planificación territorial de escala regional es lento y sus efectos prácticos todavía son escasamente visibles.

Enantioselective Synthesis of Polysubstituted Spiro-nitroprolinates Mediated by a (R,R)-Me-DuPhos·AgF-Catalyzed 1,3-Dipolar Cycloaddition

The synthesis of constrained spirocycles is achieved effectively by means of 1,3-dipolar cyclodditions employing α-imino γ-lactones as azomethine ylide precursors and nitroalkenes as dipolarophiles. The complex formed by (R,R)-Me-DuPhos 18 and AgF is the most efficient bifunctional catalyst. Final spiro-nitroprolinates cycloadducts are obtained in good to moderate yields and both high diastereo- and enantioselectivities. Density functional theory (DFT) calculations supported the expected absolute configuration as well as other stereochemical parameters.

Tiburzio Spannocchi’s project for the fortifications of Fuenterrabía in 1580

Fuenterrabía (Hondarribia) is a town located on the Franco-Spanish border. Between the 16th and 19th centuries it was considered to be one of the most outstanding strongholds in the Basque Country due to its strategic position. The bastion system of fortification was extremely prevalent in this stronghold. It was one of the first Spanish towns to adopt the incipient Renaissance designs of the bastion. The military engineers subsequently carried out continuous fortification projects that enabled the structure to withstand the advances being made in artillery and siege tactics. After the construction of the citadel of Pamplona had begun in 1571, following the design of the prestigious military engineer, Jacobo Palear Fratín and being revised by Viceroy Vespasiano Gonzaga, the aforementioned engineer undertook an ambitious project commissioned by Felipe II to modernise the fortifications of Fuenterrabía. Neither the plans nor the report of this project have been conserved, but in the year 2000, César Fernández Antuña published the report written by Spannocchi on the state of the fortifications of Fuenterrabía when he arrived to the Spanish peninsula, discovered in the Archivo Histórico Provincial de Zaragoza. This document conducts an in-depth analysis of Spannocchi’s project and how it was related to Fratín’s previous project. It concludes that this project encountered problems in updating the new bastions at the end of the 16th century, and identifies the factors which prevented the stronghold from being extended as was the case in Pamplona after Fratín’s project.

Cultural Politics of Resilience in Kingston, Jamaica

Recently, resilience has become a catchall solution for some of the world’s most pressing ecological, economic and social problems. This dissertation analyzes the cultural politics of resilience in Kingston, Jamaica by examining them through their purported universal principles of adaptation and flexibility. On the one hand, mainstream development regimes conceptualize resilience as a necessary and positive attribute of economies, societies and cultures if we are to survive any number of disasters or disturbances. Therefore, in Jamaican cultural and development policy resilience is championed as both a means and an end of development. On the other hand, critics of resilience see the new rollout of resilience projects as deepening neoliberalism, capitalism and new forms of governmentality because resilience projects provide the terrain for new forms of securitization and surveillance practices. These scholars argue that resilience often forecloses the possibilities to resist that which threatens us. However, rather than dismissing resilience as solely a sign of domination and governmentality, this dissertation argues that resilience must be understood as much more ambiguous and complex, rather than within binaries such as subversion vs. neoliberal and resistance vs. resilience. Overly simplistic dualities of this nature have been the dominant approach in the scholarship thus far. This dissertation provides a close analysis of resilience in both multilateral and Jamaican government policy documents, while exploring the historical and contemporary production of resilience in the lives of marginalized populations. Through three sites within Kingston, Jamaica—namely dancehall and street dances, WMW-Jamaica and the activist platform SO((U))L HQ—this dissertation demonstrates that “resilience” is best understood as an ambiguous site of power negotiations, social reproduction and survival in Jamaica today. It is often precisely this ambiguous power of ordinary resilience that is capitalized on and exploited to the detriment of vulnerable groups. At once demonstrating creative negotiation and reproduction of colonial capitalist social relations within the realms of NGO, activist work and cultural production, this dissertation demonstrates the complexity of resilience. Ultimately, this dissertation draws attention to the importance of studying spaces of cultural production in order to understand the power and limits of contemporary policy discourses and political economy. 

Discurso inaugural; su crítica y au defensa.

At head of title: Academia venezolana correspondiente.

The Star collection of instrumental music; arranged for wind and string instruments, and for the use of small bands and orchestras.

Contains arrangements of songs, selections from operas, dances, etc.